Ceramic silica (SiO(2)) hybrid nanofibers were prepared by electrospinning of solutions containing biocompatible polymer and modified silica precursors. The new hybrid nanofibers are based on polyethylene oxide (PEO) and a new solution of modified sol-gel particles of mixture containing tetraethoxysilane (TEOS) and 3-glycidyloxypropyltriethoxysilane (GPTEOS) in a weight ratio of 3:1. Adding high-molecular-weight PEO into the silica sol is found to enhance the formation of the silica nanofibers and leads to reduce the water-soluble carrying polymer down to 1.2%wt. Transmission electron microscopy (TEM) and attenuated total reflection fourier transformation infrared ATR-FTIR measurements are suggested that PEO is encapsulated by the silica component. This excellent formulation renders electrospinning of SiO(2) a robust process for an easy production of controllable silicate nanofibrous matrices. For instance, nanofibers with average diameter down to 400 nm are accessible by varying the weight ratio between the polymer and the inorganic precursor. These are reduced to 120 nm after the pyrolysis process. Moreover, the surface of the nanofibers could be easily modified, either by Al(3+) leading to aluminium silicate coatings, or by incorporation of Ca(2+) ions and subsequent bioactive hydroxyl carbonate apatite (HAP) formation. These hybrid silica nanofibers are possess a unique collective properties can have a great impact either in high-temperature reinforced materials and filtration or in biomedical applications such as in dentistry and bone tissue engineering.